About this Author

College chemistry, 1983

The 2002 Model

After 10 years of blogging. . .

Derek Lowe, an Arkansan by birth, got his BA from Hendrix College and his PhD in organic chemistry from Duke before spending time in Germany on a Humboldt Fellowship on his post-doc. He's worked for several major pharmaceutical companies since 1989 on drug discovery projects against schizophrenia, Alzheimer's, diabetes, osteoporosis and other diseases.
To contact Derek email him directly: derekb.lowe@gmail.com
Twitter: Dereklowe

April 19, 2013

Not the Usual Morning Around Here

Posted by Derek

Things are a bit. . .unusual around here today. I'm home; my company (and others in Cambridge) called about 6 AM to tell all employees to stay put. What with mass transit shut down and everyone off the streets, I can see the point! And truth be told, I feel a bit odd, knowing that the gunfire, etc. last night started a few blocks from where I work. This is all happening miles to the east of where I live, but it still looks like a good day to stay off the roads. . .

All thoughts and prayers to the MIT community after the heroic deeds of the MIT officer. Cambridge/Boston and the surrounding towns were my home for many years and it has been a horrifying week to watch from afar. I hope this is SAFELY ended soon...

I worked at various companies in Kendal Sq, literally across Main St. from the shooting site, for about 15 years. For 20 years I lived just over a mile from "ground zero" in Watertown (we moved a few years ago, now its about 3 miles away - close enough that helicopters rattle the windows at intervals).

To pick another, more distant disaster, care to comment on the "energetic event" in West, Texas? There has been a fair amount of debate by armchair chemists about the low flammability of the anhydrous, and how detonation could have been triggered in the nitrate. Would appreciate a professional opinion.

In typical Texas "zoning is for commies" they placed schools, etc literally across the street from a facility storing 27 tons of anhydrous ammonia, and an unknown (but given the season, enough that they had to store some of it outside) amount of granular ammonium nitrate.

No berms separating the nitrate stores from the anhydrous tanks. Never mind the NFPA's 1500' with barricades, 2000' without. Oh yea, and the middle school across the street got to do a "not a drill" evacuation back in Feb when someone noticed a fire on the grounds. Said fire turned out to be employees disposing of wooden pallets and brush by way of an open bonfire...

#7 I certainly do appreciate the Texas view of reality, but as to the topic of detonation of stored ammonium nitrate, several points need to be emphasized. First, granular ammonium nitrate doesn't detonate when treated with #2 diesel. It needs to be in a prilled form. No one in there right mind would store such a form. The tragedy in Galveston harbor in the late '40's, the largest loss of life industrial accident in US history, was a result of paraffin coating of fertilizer, since ammonium nitrate is very deliquescent. Up 'till then, it was not common knowledge that "ANFO" had such explosive potential. Any ammonium nitrate on site probably contributed to the unfortunate oxidative potential to what was burning to begin with.

#7 I certainly do appreciate the Texas view of reality, but as to the topic of detonation of stored ammonium nitrate, several points need to be emphasized. First, granular ammonium nitrate doesn't detonate when treated with #2 diesel. It needs to be in a prilled form. No one in there right mind would store such a form. The tragedy in Galveston harbor in the late '40's, the largest loss of life industrial accident in US history, was a result of paraffin coating of fertilizer, since ammonium nitrate is very deliquescent. Up 'till then, it was not common knowledge that "ANFO" had such explosive potential. Any ammonium nitrate on site probably contributed to the unfortunate oxidative potential to what was burning to begin with.

In the spirit of trying to lighten the mood, I just saw an article that mentioned nitrogen triiodide. And that got me wondering about nitrogen trifluoride. Alas, that one is far better behaved than the other trihalides.

Why should this be? Why is fluorine so much worse than chlorine, or iodine, but then, with nitrogen, the lighter the compound the not as bad it is?

I should either look into that, or putting up a comparison of all the alkali-halogens.

To put things in perspective, the Boston Marathon terror attack killed 3. HPV kills a thousand times that (from cervical cancer) in the US every year & flu kills 1-10 thousand times as many. Terrorism is about the last thing people should worry about.

I agree. No offense to the people of Boston, and Derek, and all the zillions of reporters and news shows that have ties and immediate access to the Boston neighborhoods, but I think far more lessons can be learned and exposure should be driven to the West, Texas event.

The Boston bombing, since it is getting vastly more media coverage, will likely generate vastly more legislative and regulatory response. That response, since we don't have a clue why people choose to do this, can't or shouldn't try to control the thoughts and speech of others enough to prevent, and so on, is liable to be ineffective or overreaching.

In contrast, the tragedy in Texas should be entirely preventable, in terms of inspectors who should KNOW what to ask about and look for in facilities storing fertilizer, and zoning requirements that should demand a certain amount of space between potential explosion hazards and schools and nursing homes and houses. Existing regulations that should have been followed about notifying firefighters about hazards. There are so many things that can and should be changed there, for the state of Texas and perhaps best practices and information that can be used nationally, and those changes can be relatively simple and need not be onerous.

Both are tragedies, and my sympathies go out to the survivors in both. It's just unfortunate that the one we can't do much about is driving the news cycle, and the one we should do much about is getting ignored. (That's from my perspective in the South, by the way. I'm slightly closer to West, TX than Boston, MA. It may not be clear in the northeast how much that story dominates the news elsewhere in the country.)

I'm not a chemist, but guess is its simple: fluorine bonds too strongly. The N might want to be an N2 gas, but the F really, really wants to be bonded to it, and the F gets its way.

#12-

This is true but irrelevant. Intent matters a *lot*, and one intentional homicide is more damaging to society than a much larger number of accidental/natural deaths. HPV and the flu don't grind away at the rule of law.

Yeah, #15's comment wasn't too helpful. And the thing is, I'd guess that it really is the N-F bond strength in this case, so #14 metaphysician is on the right track. Look at the carbon-halogen compounds: alkyl iodides are most reactive, whereas the fluorocarbons can hardly be budged. I see that NF3 is the only one of the nitrogen trihalides whose formation is not endothermic, so the N-F bond really does seem to be worth something.

But it's not that all N compounds want to be N2 gas, although that's certainly a thermodynamic sink. Amines and the like are perfectly stable compounds; there's no good reaction pathway to get them back to N2. That's as opposed to polyaza compounds, where there most certainly is one - and if it's there, they'll be glad to take it.

My grandfather was a firefighter in Orange, TX in 1947. He was on his way to Texas City when those shiploads of ammonium nitrate blew up -- had he got there five minutes sooner he might have been among those killed.

I was shocked to learn there were apartment buildings and a nursing home so close to a fertilizer plant. That should not have been allowed.

I assume I'm just filling in the implications of 18, but since the F-F bond of F2 is so weak, there's not as much reason for it to go back to N2 and F2, and unless there a good reductant around which can better satisfy F's desire for electrons, there's not all that much there that's going to make F happy.

Could the symmetry and number of Fs be helpful? The dipole moment and charge distribution shouldn't be as bad as for OF2. Another possibility is that N's electronegativity is low enough that it's willing to give up electrons to F, while O is more electronegative and doesn't really want to share anything. In addition, F and N are at least in the same row (although that doesn't help O) so there aren't any heinous orbital mismatches.

I don't what you could do to prevent Boston, without changing what the US is for the worse. TX was preventable if someone (at the company or in the city or state or federal governments) cared.

#22 - or at the company's insurer. It seems like insurance companies aren't paying much (if any) attention to safety at hazardous operations they insure. Why not? They should be the ones exercising oversight since they're the ones on the hook when the plant/oil rig/mine goes boom.

Terrorist attacks like Boston can't be prevented, but the response to it actually encourages more terrorism. The object of terrorism is to attract attention & cause disruption. A small scale attack (equivalent to a bad traffic accident) was turned into a front page story and shutting down Boston was a comical overreaction that caused more disruption than the terrorists themselves. If you want to discourage terrorism, ignore it.

What an unfortunate display of overactive left brains. No worse than a traffic accident? Two bombs intentionally built for maximum destruction that blew people's legs off, killed an 8-year old child and others? In Texas, 14 people killed, 60 unaccounted for? Please get your heads out of your chemical hoods and learn how to exhibit some human empathy.

The only thing that could have been done to prevent Boston is increase the awareness of folks. If something seems not right, report it... The uncle of the suspects went on national television saying that he severed ties to them because they were no good. Yet noone in the US reported their behavior before it was too late. At least one victim saw the placement of a bag. People need to not feel afraid to speak up when they see something that doesn't feel right. Yet people are afraid of speaking up for fear of being labeled discriminatory if they turn out to be wrong.

America is overly politically correct. Just look to the treatment of the Fort Hood "work place violence" criminal if you doubt political correctness has gone too far. Some Europeans fear to talk with minority groups in US for fear of 'being sued'. The only way to stop terrorism is to ignore those who label others racist or sexist or ageist or discriminatory at a drop of a hat.

@25 The Russians told the FBI about the older brother and they did not prevent this. The reports said the younger brother put the bag down just a few seconds before he blew it up; just long enough for him to get out of blast range. The people at the scene could not have prevented this, but maybe the FBI could have.

gippgig, regarding comments 12 and 23: I take your point that the american press tends towards sensationalism in cases like this, which could theoretically encourage more attacks, and so it would be constructive to talk amongst the country as a whole about what a correct response should be. However, the bad coverage does not negate the fact that it was indeed terrifying to wonder whether family and friends were ok, whether additional bombs might be placed somewhere, whether it's safe to ride the subway, etc., as well as the more general unhappy discovery that a city that has been safe for a long time and which caused no particular provocation to become otherwise can still be the target of lunatics. I also empathize with the hardships faced by those dying from diseases, etc., but their hardship doesn't negate our experience. Your comments are extremely insensitive.

#27: "a city that has been safe for a long time"? No, it hasn't! How many deaths excluding natural causes occur in Boston in a year? I don't know, but it is probably so much higher than 3 that the attack had no significant effect on the overall safety of the city.

I'm not entirely sure that the law enforcement reaction was not exactly what any terrorist would want: the city was crippled, there was tens of millions in lost business, and tremendous inconvenience to everybody who lived or worked in Boston and its immediate suburbs or had to travel through them. A person can cause a tremendous amount of disruption without doing much more than issuing credible threats. A number of years ago (actually, it was 2001), I worked at a building in New York City that started to get bomb threats right around Veterans' Day, 2001. Somebody started by calling in a threat at about 2:00pm, resulting in the building being evacuated (20 floors, with offices on all but the ground floor, probably 250 employees per floor). Police came, checked building, found no bomb. Next morning at 10:00am, a the same call. Building evacuated.. Two in the afternoon, the same day... continued for about eight weeks, until an arrest. No bomb -- it was a completely empty threat -- but the inconvenience and expense was significant.

And yet, there is no choice but to respond, because the alternative is give those who would wage war upon the rule of law free reign to commit whatever violence they wished. That is the fundamental difference between a murderer and a terrorist: a murderer only attacks his victim. A terrorist is attacking society.